Chromatography / Isothermal / Volatility / Bromides / Adsorption Summary. The Heavy Element Volatility Instrument (HEVI), an on-line isothermal gas chromatography system, has been used to separate the volatile bromide compounds of the group 4 elements Zr and Hf and the transactinide Rf according to their volatilities, and to provide data on the gas phase chemical properties of very short-lived isotopes in amounts as low as a few atoms. For these studies 261 Rf was produced via the 248 Cm( 18 O, 5n) reaction. 165Ϫ167 Hf was produced via the reaction nat Eu( 19 F, xn), and 85 Zr was produced via the nat Cu( 28 Si, 3p3n) reaction. The half-life for 261 Rf was measured to be 75Ϯ7 seconds.A Monte Carlo code was used to deduce the enthalpy of adsorption (∆H a ) from the observed volatility and parameters of the chromatography system. The resulting adsorption enthalpies for the Zr, Hf, and Rf tetrabromides are:Ϫ108Ϯ 5 kJ · mol Ϫ1 , Ϫ113 Ϯ5 kJ · mol Ϫ1 and Ϫ87Ϯ 7 kJ · mol Ϫ1 , respectively.Volatilities of the group 4 bromides support the conclusion from previous results for the group 4 chlorides that Rf deviates from the trend expected by simple extrapolation of the properties of its lighter homologs in the periodic table. The group 4 bromides are also observed to be less volatile than their respective chlorides, as predicted by relativistic calculations.